[(η(5)-C5H5)Fe(CO)(PPh3)(S(CH2CH=CH2)2)]BF4 | 182496-34-0

• 英文名称: [(η(5)-C5H5)Fe(CO)(PPh3)(S(CH2CH=CH2)2)]BF4
• CAS: 182496-34-0
• 化学式: BF₄*C₃₀H₃₀FeOPS
• 分子量: 612.259
• InChiKey: DIUCFGGELSXQIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(η(5)-C5H5)Fe(CO)(PPh3)(S(CH2CH=CH2)2)]BF4 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 以92%的产率得到(η(5)-C5H5)Fe(CO)(PPh3)(SCH(CH=CH2)CH2CH=CH2)
  参考文献：
  名称：

  Diallyl Sulfide Complexes of Chiral Iron and Ruthenium Lewis Acids:  Ylide Generation and Diastereoselective [2,3] Sigmatropic Rearrangements To Give Thiolate Complexes with New Carbon Stereocenters

  摘要：

  Reactions of the racemic iron diallyl sulfide complex [(eta(5)-C5H5)Fe(CO)(PPh(3))(S(CH2-CH=CH2)(2))](BF4-)-B-+ and t-BuOK (CH2Cl2 or THF, -80 to -60 degrees C) give the thiolate complex (eta(5)-C5H5)Fe(CO)(PPh(3))(SCH(CH=CH2)CH2CH=CH2) (65-92%) as 77-68:23-32 mixtures of SS,RR/SR,RS Fe,SC diastereomers. Reactions of the enantiomerically pure ruthenium diallyl sulfide complexes [(eta(5)-C5H5)Ru(S,S-chiraphos)(S(CH(2)CR=CH2)(2))](PF6-)-P-+ (5(+)PF(6)(-); R = a, H; R = b, CH3) and t-BuOK(CH2Cl2, -98 degrees C) give the thiolate complexes (eta(5)-C5H5)Ru(S,S-chiraphos)(SCH(CR=CH2)CH(2)CR=CH2) as 78:22 (8a, > 99%) and 87:13 (8b, 97%) mixtures of chromatographically separable SSS/SSR PC,P'C',SC diastereomers. These transformations likely involve intermediate sulfur ylides as described in the title. Reactions of 8a,b with CH3I or PhCH(2)I and then NaI (acetone, reflux) give, via cationic methyl or benzyl sulfide complexes, enantiomerically enriched R'SCH(CH(2)CR=CH2)CR=CH2 (R/R' = H/CH3, 75%; CH3/CH3, 71%; H/PhCH(2) and CH3/PhCH(2), >99%) and (eta(5)-C5H5)Ru(S,S-chiraphos)(I) (6, greater than or equal to 97%). Complex 6 is readily recycled to enantiomerically pure 5a,b(+)PF(6)(-) (NH4+PF6-, CH3OH, S(CH(2)CR=CH2)2; 94-97%).

  DOI：

  10.1021/om960541q
• 作为产物：
  描述：

  二烯丙基硫醚 、 cyclopentadienyl iron carbonyl triphenylphosphine iodide 、 silver tetrafluoroborate 以 四氢呋喃 、 二氯甲烷 为溶剂， 以80%的产率得到[(η(5)-C5H5)Fe(CO)(PPh3)(S(CH2CH=CH2)2)]BF4
  参考文献：
  名称：

  Diallyl Sulfide Complexes of Chiral Iron and Ruthenium Lewis Acids:  Ylide Generation and Diastereoselective [2,3] Sigmatropic Rearrangements To Give Thiolate Complexes with New Carbon Stereocenters

  摘要：

  Reactions of the racemic iron diallyl sulfide complex [(eta(5)-C5H5)Fe(CO)(PPh(3))(S(CH2-CH=CH2)(2))](BF4-)-B-+ and t-BuOK (CH2Cl2 or THF, -80 to -60 degrees C) give the thiolate complex (eta(5)-C5H5)Fe(CO)(PPh(3))(SCH(CH=CH2)CH2CH=CH2) (65-92%) as 77-68:23-32 mixtures of SS,RR/SR,RS Fe,SC diastereomers. Reactions of the enantiomerically pure ruthenium diallyl sulfide complexes [(eta(5)-C5H5)Ru(S,S-chiraphos)(S(CH(2)CR=CH2)(2))](PF6-)-P-+ (5(+)PF(6)(-); R = a, H; R = b, CH3) and t-BuOK(CH2Cl2, -98 degrees C) give the thiolate complexes (eta(5)-C5H5)Ru(S,S-chiraphos)(SCH(CR=CH2)CH(2)CR=CH2) as 78:22 (8a, > 99%) and 87:13 (8b, 97%) mixtures of chromatographically separable SSS/SSR PC,P'C',SC diastereomers. These transformations likely involve intermediate sulfur ylides as described in the title. Reactions of 8a,b with CH3I or PhCH(2)I and then NaI (acetone, reflux) give, via cationic methyl or benzyl sulfide complexes, enantiomerically enriched R'SCH(CH(2)CR=CH2)CR=CH2 (R/R' = H/CH3, 75%; CH3/CH3, 71%; H/PhCH(2) and CH3/PhCH(2), >99%) and (eta(5)-C5H5)Ru(S,S-chiraphos)(I) (6, greater than or equal to 97%). Complex 6 is readily recycled to enantiomerically pure 5a,b(+)PF(6)(-) (NH4+PF6-, CH3OH, S(CH(2)CR=CH2)2; 94-97%).

  DOI：

  10.1021/om960541q